TW202033566A - Ethylenic unsaturated resin composition and photosensitive resin composition - Google Patents

Abstract

Provided is a resin composition having a low residual amount of polymerization inhibitor, and having high transparency, thermal yellowing resistance, and dispersibility of fine particles, including coloring materials. This ethylenic unsaturated resin composition contains an ethylenic unsaturated resin (A), carbon clusters (c), and a solvent (B). The carbon clusters (c) are fullerene and/or a soot-like substance, and the carbon cluster (c) content is 0.00001-10 parts by mass per 100 parts by mass of the ethylenic unsaturated resin (A).

Description

Ethylene unsaturated resin composition and photosensitive resin composition

The present invention relates to an ethylenically unsaturated resin composition and a photosensitive resin composition.

Acrylic resins are used in various fields because of their excellent transparency, weather resistance, and balanced mechanical properties. Recently, a document discloses that by using a photosensitive resin composition containing a resin introduced with ethylenic unsaturated groups, through coating, exposure, and development steps, the formation of black column spacers as members for displays, etc. (Patent Literature 1). Regarding a method of introducing an ethylenically unsaturated group into a resin, there is a document that discloses a method of reacting an epoxy group-containing resin and a carboxyl group-containing ethylenically unsaturated compound in the presence of a polymerization inhibitor and a catalyst. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2017/204079

[The problem to be solved by the invention]

In recent years, due to the improved performance required for displays, acrylic resins are also regarded as important for high heat yellowing resistance and high pigment dispersibility. Therefore, it is desired to reduce the amount of inhibitor or residual catalyst that is more than the polymerization inhibitor required for storage.

In order to solve the above-mentioned problems, the present invention can be efficiently synthesized using a small amount of carbon clusters, and an ethylenically unsaturated resin composition can be obtained. That is, the object of the present invention is to provide an ethylenically unsaturated resin composition containing a small amount of carbon clusters, and even to provide a photosensitive resist with high heat yellowing resistance, high dispersion of colorant-containing particles, and excellent pattern shape resists.性resin composition. [Means used to solve the problem]

That is, the present invention is represented by the following [1] to [13]. [1] An ethylenically unsaturated resin composition characterized by containing: ethylenically unsaturated resin (A), carbon clusters (c) and solvent (B), wherein the carbon clusters (c) are in the form of fullerenes and soot At least one of the substances has a content of 0.00001-10 parts by mass relative to 100 parts by mass of the aforementioned ethylenically unsaturated resin (A). [2] The ethylenically unsaturated resin composition as in [1], wherein the aforementioned ethylenically unsaturated resin (A) is an ethylenically unsaturated compound (m-2) containing a carboxyl group and added to an epoxy-containing The epoxy group of the copolymer (P1), the polybasic acid anhydride (d) is added to the hydroxy group generated by the epoxy group opening, and the ethylenically unsaturated resin (A1), and the aforementioned epoxy group-containing copolymer (P1) is a structural unit derived from epoxy-containing (meth)acrylate (m-1), and a polymerizable monomer (m-) selected from a bridged cyclic hydrocarbon group having 10 to 20 carbons 3) The structural unit and a copolymer of at least one of the group consisting of the structural unit from the polymerizable monomer (m-4) represented by the following chemical formula (1),

(X and X'in the formula (1) are each independent and represent a hydrogen atom, a linear or branchable hydrocarbon group with 1 to 4 carbons, R1 and R2 are each independent, and each is a hydrogen atom, a carboxyl group or a carbon that may have a substituent The hydrocarbon group of 1-20 may also adopt a cyclic structure connecting R1 and R2). [3] The ethylenically unsaturated resin composition as in [1], wherein the ethylenically unsaturated resin (A) is a carboxyl group-containing copolymer (P2) that is ring-opened and added to an epoxy-containing ethylenic unsaturated compound (m-1) An unsaturated group-containing ethylenically unsaturated resin (A2) having a hydroxyl group composed of epoxy groups, and the aforementioned carboxyl-containing copolymer (P2) contains an ethylenically unsaturated compound derived from a carboxyl group The structural unit of (m-2), and the structural unit selected from the polymerizable monomer (m-3) having a bridged cyclic hydrocarbon group having 10 to 20 carbons, and the polymerization represented by the following chemical formula (1) A copolymer of at least one of the group consisting of the structural unit of the sexual monomer (m-4),

(X and X'in the formula (1) are each independent and represent a hydrogen atom, a linear or branchable hydrocarbon group with 1 to 4 carbons, R1 and R2 are each independent, and each is a hydrogen atom, a carboxyl group or a carbon that may have a substituent The hydrocarbon group of 1-20 may also adopt a cyclic structure connecting R1 and R2). [4] The ethylenically unsaturated resin composition as in [1], wherein the ethylenically unsaturated resin (A) is an ethylenically unsaturated compound (m-2) containing a carboxyl group and added to the epoxy resin (P3 The epoxy group of ), and an ethylenically unsaturated resin (A3) obtained by adding a polybasic acid anhydride (d) to the hydroxyl group generated by the opening of the epoxy group, and The aforementioned epoxy resin (P3) is At least one selected from the group consisting of novolac epoxy resin (P3-1), bisphenol epoxy resin (P3-2), and bifunctional epoxy resin (P3-3) having a biphenyl skeleton. [5] The ethylenically unsaturated resin composition as in [1], wherein the ethylenically unsaturated resin (A) is a resin (P4) containing a carboxyl group by ring-opening addition to an ethylenically unsaturated compound containing an epoxy group ( m-1) an ethylenically unsaturated resin (A4) with a hydroxyl group composed of epoxy groups, and The aforementioned carboxyl group-containing resin (P4) is a carboxyl group-containing resin obtained by reacting an epoxy resin (P3) with a polyfunctional carboxylic acid (e), The aforementioned epoxy resin (P3) is At least one selected from the group consisting of novolac epoxy resin (P3-1), bisphenol epoxy resin (P3-2), and bifunctional epoxy resin (P3-3) having a biphenyl skeleton. [6] The ethylenically unsaturated resin composition as in [1], wherein the aforementioned ethylenically unsaturated resin (A) is Polybasic acid anhydride (d) is added to the ethylenic unsaturated resin (A5) of the ethylenic unsaturated resin (A2) as in [3], or An ethylenic unsaturated resin (A6) in which a polybasic acid anhydride (d) is added to the hydroxyl group of the ethylenic unsaturated resin (A4) as in [5]. [7] The ethylenically unsaturated resin composition according to any one of [1] to [6], wherein the aforementioned carbon cluster (c) is an unsubstituted fullerene. [8] The ethylenically unsaturated resin composition according to any one of [1] to [7], which contains substantially no polymerization inhibitor other than the carbon cluster (c). [9] The ethylenically unsaturated resin composition according to any one of [1] to [8], which further contains a reactive diluent (D). [10] A photosensitive resin composition containing the ethylenically unsaturated resin composition according to any one of [1] to [9] and a photopolymerization initiator (E). [11] The photosensitive resin composition of [10], which further contains a colorant (F), The colorant (F) is at least one selected from the group consisting of dyes and pigments. [12] The photosensitive resin composition according to [10] or [11], which contains substantially no polymerization inhibitor other than the carbon cluster (c). [13] A photoresist using the photosensitive resin composition of any one of [10] to [12]. [Effects of Invention]

According to the present invention, it is possible to provide an ethylenically unsaturated resin composition containing a small amount of carbon clusters, high transparency, high heat yellowing resistance, and high dispersibility of colorant-containing fine particles, and a photosensitive resin composition using the same.

The present invention will be described in detail below. [Ethylene Unsaturated Resin Composition] The ethylenically unsaturated resin composition of the present invention contains ethylenically unsaturated resin (A), carbon cluster (c) and solvent (B). The aforementioned carbon cluster (c) is at least one of fullerene and soot-like substance. The content of the carbon cluster (c) is 0.00001 to 10 parts by mass relative to 100 parts by mass of the ethylenically unsaturated resin (A). The aforementioned carbon cluster (c) is preferably an unsubstituted fullerene. In addition, the ethylenically unsaturated resin composition of the present invention may not substantially contain a polymerization inhibitor other than the carbon cluster (c). "Substantially free" means that the content of a polymerization inhibitor other than the carbon cluster (c) is preferably 0.05 parts by mass or less, preferably 0.01 parts by mass or less, relative to 100 parts by mass of the ethylenically unsaturated resin (A).

The resin composition of the present invention may further contain a reactive diluent (D).

[Carbon cluster (c)] By containing the carbon cluster (c), the ethylenically unsaturated resin composition of the present invention can prevent colloidization caused by the polymerization of the double bond of the ethylenically unsaturated resin (A), and can improve storage stability. In addition, by using the carbon cluster (c) in the photosensitive resin composition containing the photopolymerization initiator (E) described later, it does not adversely affect the curability, and it is possible to obtain heat-resistant yellowing resistance or dispersion of fine particles containing colorants. A photosensitive resin composition having excellent properties and capable of obtaining a photoresist having an excellent pattern shape.

Carbon clusters (c) are clusters or fine particles formed by aggregation of several to hundreds of atoms or molecules. For the size of the carbon cluster (c), the maximum particle size is preferably 300 nm or less, and more preferably 100 nm or less. The carbon clusters (c) may agglomerate primary particles, and the size of the primary particles affects the dispersion of the carbon clusters (c). Therefore, the maximum particle size referred to here is the maximum particle size of the primary particles. The carbon cluster (c) of the present invention is a fullerene or soot-like substance.

The fullerenes used in the present invention are known to have carbon numbers of 60, 70, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96 and the like with carbon numbers of about 60 to 120. Leene. In the present invention, the carbon number is not particularly limited. From the viewpoint of easy availability and excellent dispersibility, carbon number 60 (C60) and carbon number 70 (C70) are preferred. In addition, fullerenes containing heterogeneous atoms such as scandium (Sc), lanthanum (La), cerium (Ce), titanium (Ti), and nitrogen (N) can also be used. In addition, fullerene oxides, fullerene oxides (C60) ₂ O or fullerene addition products (C60-C60, C70-C60, C70-C70, etc.) can also be used. .

The soot-like substance used in the present invention is preferably coal that is by-produced during fullerene production. Crude fullerenes produced during the manufacturing process of fullerenes are also included. After the fullerene solvent is extracted and removed from the crude fullerene, the residue contains more soot-like substances. This soot-like carbon substance has a structure in which a 5-membered ring and a 6-membered ring are bonded like fullerenes, and contains amorphous carbon molecules without a closed shell. Examples of methods for producing fullerenes that produce soot-like substances include resistance heating methods, arc discharge methods, microwave methods, high-frequency heating methods, CVD methods, thermoplasma methods, combustion methods, laser methods, and thermal decomposition methods. All of them are manufactured in an environment with a pressure of 800hPa or less. The soot-like carbon material can be obtained, for example, by burning a hydrocarbon raw material and an oxygen-containing gas in a reduced pressure environment in the case of a gas combustion method. As the hydrocarbon raw material, aromatic hydrocarbons such as toluene and benzene can be used. The decompression condition is set at 3～800hPa, and the heating condition is set at 1600℃～2000℃.

If the hydrocarbon feedstock and oxygen-containing gas are combusted under the aforementioned reduced pressure environment, hydrogen will escape from the hydrocarbon feedstock. Here, the mixing ratio of the hydrocarbon feedstock to the oxygen-containing gas is 2.5 to 3.5 in terms of equivalent ratio, and it is preferable to increase the amount of the hydrocarbon feedstock. In this way, the reaction can be incompletely burnt. If the reaction is completely burned, the carbon in the hydrocarbon feedstock will be combined with oxygen and will be discharged as carbon monoxide or carbon dioxide, and the carbons may become difficult to bond with each other. In addition, the equivalence ratio is to set the ratio of the amount of hydrocarbon feedstock just completely burned to the amount of oxygen as 1.

The hydrocarbon feedstock after hydrogen removal is not stable, and surrounding carbon tends to aggregate with each other. At this time, some of them will react to produce chemical bonds. The carbon compound obtained by such a process contains soot-like substances and other carbon compounds. In the soot-like substance, molecules are bonded to each other, and multiple carbons are bonded, and it contains amorphous carbon molecules that cannot become a predetermined spherical molecular structure like fullerene. The structure of this amorphous carbon molecule is the same as the partial structure of fullerenes. Examples include intermediates produced during the production of fullerenes, or structures with spherical fullerenes that are partially lacking or have no closed shell. Of carbon molecules. This amorphous carbon molecule may also be a cluster structure formed by gathering a plurality of such carbon molecules. The cluster structure includes a telescopic structure constructed in such a way that carbon molecules having a large-size unclosed shell structure enclose carbon molecules having a small-size unclosed shell structure.

The carbon cluster (c) may have a substituent as long as it does not impair the effect of dispersibility or radical capture ability. Examples of the substituent include indene, malonic acid, methyl phenylbutyrate, etc., derivatives of fullerene, including ICBA (indene double adduct), ICMA (indene adduct), PCBM (phenyl-C61- Methyl butyrate, etc.), SAM (1-methyl-1H-pyrrolobenzoic acid adduct), etc.

The addition amount of the carbon cluster (c) is 0.00001 to 10 parts by mass relative to 100 parts by mass of the ethylenically unsaturated resin (A), preferably 0.0001 to 5 parts by mass, and more preferably 0.005 to 1 part by mass. As long as it is 0.00001 parts by mass or more, the double bond polymerization of the ethylenically unsaturated resin (A) can be prevented and the composition can be colloidal. As long as it is 10 parts by mass or less, the curability will not be adversely affected when the photosensitive resin composition described later is prepared and photocured. As long as the ethylenically unsaturated resin composition finally contains the carbon cluster (c), the effect of the present invention can be obtained. In addition, if the carbon cluster (c) is added at the stage of synthesizing the ethylenically unsaturated resin (A), the carbon cluster (c) can be more effectively dispersed in the ethylenically unsaturated resin composition. The addition amount of the carbon cluster (c) used in the synthesis of the ethylenically unsaturated resin (A) is preferably 0.0001 to 0.1 parts by mass, 0.005 to 100 parts by mass of the total polymer and monomer as the material. 0.05 parts by mass is preferable. As long as the amount of carbon clusters (c) added during the reaction is 0.1 parts by mass or less, the reaction will not be hindered even when the ethylenically unsaturated resin (A) is cured by radicals. As long as it is 0.0001 part by mass or more, radicals generated in the reaction when the ethylenically unsaturated resin (A) is obtained can be sufficiently trapped, and colloidization of the ethylenically unsaturated resin (A) can be prevented.

The amount of carbon cluster (c) used is small, so from the viewpoint of convenience, etc., it is better to use unsubstituted fullerene for carbon cluster (c), which contains C60, C70 and other higher-order fullerenes. The mixed and unsubstituted fullerenes are preferred.

For the carbon cluster (c), for example, a fullerene mixture nanom mix ST (composed of C60 about 60%, C70 about 25%, and other high-order fullerenes) manufactured by Frontier Carbon can be used.

[Polymerization inhibitors other than carbon cluster (c)] Polymerization inhibitors other than the carbon cluster (c) except for the carbon cluster (c) related to the present invention are usually added to prevent colloidization caused by polymerization of the double bond introduced into the ethylenically unsaturated resin (A) The type of the polymerization inhibitor is not particularly limited, but specific examples include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and dibutylhydroxytoluene.

[Ethylene Unsaturated Resin (A)] The ethylenically unsaturated resin (A) of the present invention is not particularly limited as long as it is a resin containing an ethylenically unsaturated group, and it is preferable to combine an epoxy group-containing compound (a) with a carboxyl group-containing compound (b). ) A resin obtained by the reaction, wherein at least one of the epoxy group-containing compound (a) and the carboxyl group-containing compound (b) contains an ethylenically unsaturated group. For example, it can be obtained by a method of reacting an epoxy group-containing resin and a carboxyl group-containing unsaturated compound in the presence of a carbon cluster (c) as a polymerization inhibitor and a catalyst. Alternatively, for example, it can also be obtained by a method of reacting an epoxy group-containing unsaturated compound and a carboxyl group-containing resin in the presence of a carbon cluster (c) as a polymerization inhibitor and a catalyst.

The epoxy group-containing compound (a) related to the present invention is not particularly limited as long as it is a compound having an epoxy group. Suitable examples include the epoxy group-containing copolymer (P1) in the first embodiment described below, and the epoxy group-containing ethylenically unsaturated compound (m) in the second embodiment and fourth embodiment described below. -1) Epoxy resin (P3) in the third embodiment described later. The carboxyl group-containing compound (b) related to the present invention is not particularly limited as long as it is a compound having a carboxyl group. Suitable examples include the carboxyl group-containing ethylenically unsaturated compound (m-2) in the first embodiment and the third embodiment described later, the carboxyl group-containing copolymer (P2) in the second embodiment described later, The carboxyl group-containing resin (P4) in the fourth embodiment will be described later.

The amount of carbon cluster (c) used is, for example, 0.00001-10 parts by mass relative to the total of 100 parts by mass of the epoxy group-containing compound and the carboxyl group-containing compound, and the finally obtained ethylenically unsaturated resin composition It contains 0.00001-10 parts by mass of carbon cluster (c) with respect to 100 parts by mass of the ethylenically unsaturated resin (A).

[First implementation aspect] [Ethylene Unsaturated Resin (A1)] The ethylenically unsaturated resin (A1) of this embodiment is a carboxyl-containing ethylenic unsaturated compound (m-2) which is a carboxyl-containing compound (b), which is a ring-opening addition to an epoxy-containing compound ( a) The epoxy group of the epoxy group-containing copolymer (P1), if necessary, further polybasic acid anhydride (d) is added to the hydroxyl group generated by the epoxy group ring-opening, and a resin having an ethylenically unsaturated group . The aforementioned epoxy group-containing copolymer (P1) contains a structural unit derived from an epoxy group-containing ethylenically unsaturated compound (m-1) and is selected from those derived from bridged cyclic hydrocarbon groups having 10 to 20 carbon atoms A copolymer of at least one of the structural unit of the polymerizable monomer (m-3) and the structural unit derived from the polymerizable monomer (m-4) represented by the above chemical formula (1). The ethylenically unsaturated resin (A1) may further contain a structural unit derived from an aromatic ring-containing polymerizable monomer (m-5).

The ethylenically unsaturated resin (A1) related to this embodiment can introduce a double bond with excellent photosensitivity by containing the structural unit produced by the addition reaction of the carboxyl-containing ethylenically unsaturated compound (m-2) At the same time, by opening the epoxy group, a hydroxyl group with excellent alkali developability can be obtained. In addition, if a polybasic acid anhydride (d) is added to the obtained hydroxyl group to introduce a carboxylic acid, the alkali developability can be improved. With this structural unit, the hardened product will exhibit sufficient hardness and exhibit high solvent resistance. In addition, by not allowing all epoxy groups to react with the carboxyl group-containing ethylenically unsaturated compound (m-2), a part of the epoxy groups remains, and thermosetting properties can be exhibited at the same time.

[Epoxy-containing copolymer (P1)] The monomer (M1) that forms the epoxy group-containing copolymer (P1) related to the ethylenically unsaturated resin (A1) of this embodiment (hereinafter also referred to as "copolymer (P1)") , Comprising an epoxy-containing ethylenically unsaturated compound (m-1), and a polymerizable monomer (m-3) selected from bridged cyclic hydrocarbon groups having 10 to 20 carbon atoms and the above chemical formula (1) At least one of the group consisting of the indicated polymerizable monomer (m-4). The monomer (M1) may further include an aromatic ring-containing polymerizable monomer (m-5), other polymerizable monomers (m-6), and the like. By further having an aromatic ring-containing polymerizable monomer (m-5), an epoxy group-containing copolymer (P1) having more excellent colorant dispersibility can be obtained.

[Ethylene unsaturated compound containing epoxy group (m-1)] An epoxy-containing ethylenically unsaturated compound (m-1) (hereinafter sometimes referred to as "monomer (m-1)") as long as it does not have a carboxyl group, it has an epoxy group and an ethylenically unsaturated group The monomers are not particularly limited. Specific examples include glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexyl Methyl (meth)acrylate, its lactone adduct (for example, CYCLOMER (registered trademark) A200, M100 manufactured by DAICEL Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl-3',4' -Mono(meth)acrylate of epoxycyclohexane carboxylate, epoxy of dicyclopentenyl (meth)acrylate, epoxy of dicyclopentenoxyethyl (meth)acrylate物, etc. These epoxy group-containing ethylenically unsaturated compounds (m-1) can be used alone or in two or more types. In particular, from the viewpoint of availability and good reactivity, glycidyl (meth)acrylate is suitable.

The structural unit derived from the epoxy group-containing ethylenic unsaturated compound (m-1) and the carboxyl group-containing ethylenic unsaturated compound (m-2) described later, in order to add a photosensitive group exhibiting photocuring properties, in the present invention One form of ethylenically unsaturated resin (A1) is an essential source structure. By introducing a photosensitive base exhibiting photocurability, the cured film will exhibit sufficient hardness and exhibit high solvent resistance.

[Polymerizable monomer (m-3)] The polymerizable monomer (m-3) (hereinafter sometimes referred to simply as "monomer (m-3)]) has a bridged cyclic hydrocarbon group with 10 to 20 carbon atoms. Here, the bridged cyclic hydrocarbon, It means a compound represented by adamantane and norbornane having a structure represented by the following formula (2) or (3), and a bridged cyclic hydrocarbon group refers to the structure after removing a part of the hydrogen The remaining part of the group. In addition, the polymerizable monomer (m-3) does not include the polymerizable monomer (m-4) described later.

(In formula (2), A and B respectively represent linear or branched alkylene (including cyclic formula), and R3 represents a hydrogen atom or a methyl group. A and B may be the same or different, and the branches of A and B may be mutually exclusive The connection becomes a ring).

(In formula (3), A', B', and D each represent a linear or branched alkylene group (including cyclic formula), and R4 represents a hydrogen atom or a methyl group. A', B', and D may be the same or different, The branches of A', B', and D can be connected to each other to form a ring).

The monomer (m-3) is preferably a (meth)acrylate having a bridged cyclic hydrocarbon group with 10 to 20 carbons, and has a structure represented by adamantyl (meth)acrylate or the following formula (4) The (meth)acrylate is preferred.

(In formula (4), R5 to R7 respectively represent a hydrogen atom or a methyl group. R8 and R9 are a hydrogen atom or a methyl group, or may be connected to each other to form a saturated or unsaturated ring. The ring is preferably a 5-membered ring or a 6-membered ring Ring. * represents the bonding bond to the (meth)acryloyloxy group).

Examples of (m-3) above include dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, isocamyl (meth)acrylate, adamantyl (meth)acrylate, etc. . These can be used alone or in combination of two or more.

[Polymerizable monomer (m-4)] The polymerizable monomer (m-4) (hereinafter sometimes referred to simply as "monomer (m-4)") is a monomer represented by the following general formula (1).

(X and X'in the formula (1) are each independent and represent a hydrogen atom, a linear or branchable hydrocarbon group with 1 to 4 carbons, and R1 and R2 are each independent, and each is a hydrogen atom or a substituted carbon number 1 The hydrocarbon group of -20 may also adopt a cyclic structure connecting R1 and R2).

The monomer (m-4) is not particularly limited as long as it has a chemical structure represented by general formula (1). In the general formula (1), examples of X and X'representing a linear or branched hydrocarbon group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, iso Butyl, tertiary butyl, etc. In addition, the substituent in the optionally substituted hydrocarbon group having 1 to 20 carbons represented by R1 and R2 includes an alkoxy group and an aromatic group. Examples of R1 and R2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, tertiary pentyl, stearyl, lauryl, 2- Ethylhexyl and other linear or branched alkyl groups; cyclohexyl, tertiary butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, 2-methyl- Alicyclic groups such as 2-adamantyl groups; alkyl groups substituted with alkoxy groups such as 1-methoxyethyl and 1-ethoxyethyl groups; alkyl groups substituted with aromatic groups such as phenylaralkyl groups Alkyl and so on.

Examples of the monomer (m-4) having the chemical structure represented by the general formula (1) include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1 ] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] twelve-3-ene, 8-methyl-four ring [4.4.0.1 ^2,5 .1 ^7,10] twelve-3-ene, 8-ethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] twelve-3-ene, dicyclopentadiene Diene, tricyclo[5.2.1.0 ^2,6 ]dec-8-ene, tricyclo[5.2.1.0 ^2,6 ]dec-3-ene, tricyclo[4.4.0.1 ^2,5 ]undec-3-ene Alkene, tricyclo[6.2.1.0 ^1,8 ]undec-9-ene, tricyclo[6.2.1.0 ^1,8 ]undec-4-ene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6] dodeca-3-ene, 8-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6] twelve-3-ene, 8-ethylidene-four ring [4.4.0.1 ^2,5 .1 ^7,12] twelve-3-ene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6] twelve -3 - ene, pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13] fifteen-4-ene, pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13] Penta-3-ene and so on. These can be used alone or in combination of two or more.

The use of the monomer (m-3) and/or the monomer (m-4) contributes to smooth coating properties, high thermal decomposition resistance, and high thermal yellowing resistance of the cured film. In addition, one or both of the monomer (m-3) and the monomer (m-4) can be used.

[Polymerizable monomer containing aromatic ring (m-5)] The aromatic ring-containing polymerizable monomer (m-5) (hereinafter sometimes referred to as "monomer (m-5)") is a monomer that does not have a carboxyl group or an epoxy group, but an aromatic ring. Examples include styrene, α-methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, Aromatic vinyl compounds such as m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene, and p-acetamidostyrene; benzyl (meth)acrylate, Rosin (meth)acrylate, phenyl (meth)acrylate, cumyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy-polyethylene glycol (methyl) ) Acrylate (trade name: LIGHT ACRYLATE P-200A, manufactured by Kyoei Chemical Co., Ltd.), nonylphenoxy polyethylene glycol mono(meth)acrylate, o-phenoxybenzyl (meth)acrylate, ( M-phenoxybenzyl (meth)acrylate, p-phenoxybenzyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, biphenoxyethyl (meth)acrylate, ethoxy Alkylated ortho-phenylphenol (meth)acrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, etc. Among these, from the standpoint of elastic recovery rate, the ethylenically unsaturated resin (A1) used in the present invention has a benzyl (meth)acrylate, styrene, biphenyl skeleton, naphthalene skeleton and At least one structural unit in the group formed by the anthracene skeleton is preferable.

[Other polymerizable monomers (m-6)] The epoxy group-containing copolymer (P1) related to this embodiment can also be combined with other polymerizable monomers (m-6) other than monomers (m-1) to (m-5) (the following will also be It may be referred to as "monomer (m-6)" for short) Copolymerization. Other polymerizable monomers (m-6) are disclosed in addition to the aforementioned monomers (m-1), (m-3), (m-4), (m-5), and the monomer (m-2) described later Other copolymerizable monomers. This monomer (m-6) is generally a radically polymerizable compound having an ethylenically unsaturated group. For example, this monomer (m-6) includes dienes such as (meth)acrylates, (meth)acrylamides, maleimines, unsaturated dicarboxylic acid diesters, butadiene, etc. Class etc. Specific examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth) N-butyl acrylate, second butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate , Benzyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, (meth) Dodecyl acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methyl cyclohexyl (meth)acrylate, ethyl cyclohexyl (meth)acrylate, (meth) Rosin acrylate, allyl (meth)acrylate, tetrahydrofuran methyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, (meth)acrylic acid 3-(N,N-dimethylamino)propyl ester, naphthyl (meth)acrylate, anthracene (meth)acrylate, etc. Specific examples of (meth)acrylamide include (meth)acrylamide, (meth)acrylic acid N,N dimethylamide, (meth)acrylic acid N,N diethylamide, (meth)acrylic acid (Base) acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-diisopropylamide, (meth)acrylic acid anthrylamide, etc. Specific examples of maleimines include (meth)acrylic aniline, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and N-ethylene Vinyl compounds such as pyrrolidone and vinyl acetate; N-cyclohexyl maleimide, N-lauryl maleimide, etc. Specific examples of unsaturated dicarboxylic acid diesters include diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconic acid, and the like. These can be used alone or in combination of two or more as necessary.

[The ratio of the structure derived from each monomer in the epoxy group-containing copolymer (P1)] In the copolymer (P1) related to the present invention, its monomer (M1) contains monomer (m-1), and if necessary, it contains monomer (m-3) or monomer (m-4). , Or in the case of the monomer (m-5), the ratio derived from the structure of each monomer is a value using the molar ratio of each polymerizable monomer added for the copolymerization reaction. The blending ratio (molar ratio) of each monomer is not particularly limited. The blending ratio of the monomer (m-1) is preferably 9-70 mol%, preferably 13-65 mol%. If the blending ratio of the monomer (m-1) is 9 mol% or more, sufficient curability can be exhibited when it is made into a photosensitive resin composition. If the blending ratio of the monomer (m-1) is 70 mol% or less, the blending ratio of the monomer (m-3) and/or the monomer (m-4) is large enough to obtain the desired Ethylene unsaturated resin (A1) with heat decomposition resistance or refractive index.

In the case of using the monomer (m-3) and/or the monomer (m-4), the blending ratio is 100 relative to the total amount of the monomer (M1) of the epoxy group-containing copolymer (P1) The mol% is preferably more than 0 mol% and 40 mol% or less, and more than 0 mol% and 30 mol% or less. If the blending ratio exceeds 0 mol%, the desired thermal decomposition resistance or thermal yellowing resistance and good solubility in solvents can be obtained. In the case of using the monomer (m-5), the blending ratio is 100 mol% relative to the total amount of the monomer (M1) of the epoxy-containing copolymer (P1), and it exceeds 0 mol% and It is preferably 50 mol% or less, and more than 0 mol% and 40 mol% or less. In the case of using the monomer (m-6), the blending ratio is 100 mol% relative to the total amount of the monomer (M1) of the epoxy-containing copolymer (P1), and exceeds 0 mol% It is preferably 10 mol% or less, and more than 0 mol% and 5 mol% or less.

[Copolymerization reaction (method for producing epoxy group-containing copolymer (P1))] The epoxy group-containing copolymer (P1) related to the present invention can be produced by copolymerization of the monomer (M1). The copolymerization reaction carried out in the present invention can be carried out according to a radical polymerization method known in the technical field. For example, after dissolving the monomers used in the copolymerization in a solvent, add a polymerization initiator to the solution, and react at 50 to 140°C, preferably 60 to 130°C, for 1 to 20 hours, preferably 1 ~12 hours. In addition, the monomer and the polymerization initiator used in the copolymerization may be dropped into a solvent adjusted to 50 to 140°C and allowed to react at the same time.

The solvent that can be used in this copolymerization reaction is not particularly limited as long as it is a solvent that is inactive for radical polymerization, and a commonly used organic solvent can be used. As the copolymerization reaction solvent, the solvent for addition reaction described later can be used.

The amount of solvent used in this copolymerization reaction is not particularly limited. When the total amount of monomers used in the copolymerization is 100 parts by mass, it is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass. Mass parts. In particular, by setting the amount of the solvent used to be 1000 parts by mass or less, the decrease in the molecular weight of the copolymer (P1) caused by chain transfer can be suppressed, and the viscosity of the copolymer (P1) can be controlled in an appropriate range. In addition, by setting the amount of the solvent used at 30 parts by mass or more, abnormal polymerization reactions can be prevented, the polymerization reaction can proceed stably, and the copolymer (P1) can also be prevented from coloring or colloidization.

The polymerization initiator that can be used in this copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and generally used organic peroxide catalysts or azo compounds can be used. Specifically, azobisisobutyronitrile, azobisisovaleronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), azobis(2-methylpropionic acid) ) Dimethyl, benzyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-tertiary butyl peroxide, tertiary butyl peroxybenzoate, tertiary hexyl peroxide Oxybenzoate, tertiary butylperoxy-2-ethylhexanoate, tertiary hexylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy -2-ethylhexanoate and so on. These can be used alone or in combination of two or more, and it is desirable to select a radical polymerization initiator with an appropriate half-life in accordance with the polymerization temperature.

The blending amount of the polymerization initiator used in this copolymerization reaction is not particularly limited. When the total amount of monomers used in the copolymerization is 100 parts by mass, it is generally 0.5-20 parts by mass, preferably 1.0 ~10 parts by mass.

[Ethylene unsaturated compound containing carboxyl group (m-2)] Ethylene unsaturated compound (m-2) containing a carboxyl group (hereinafter sometimes referred to as "monomer (m-2)") as long as it does not have an epoxy group, it has reactivity with an epoxy group among the acid groups The monomer of particularly good carboxyl group and ethylenically unsaturated group is not particularly limited. For example, unsaturated monobasic acid or unsaturated dibasic acid monoester can be mentioned. Unsaturated monobasic acids, including (meth)acrylic acid, itaconic acid, crotonic acid, cinnamic acid, 2-(meth)acryloxyethyl succinic acid, 2-(meth)acryloxyethyl Phthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, propioic acid, cinnamic acid, α -Unsaturated carboxylic acids such as cyanocinnamic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, and monoethyl itconate. Examples of unsaturated dibasic acid monoesters include monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, and monoethyl itconate. These carboxyl group-containing ethylenically unsaturated compounds (m-2) can be used alone or in two or more types. Among these, (meth)acrylic acid is preferred from the viewpoint of availability and reactivity.

The reaction ratio of the carboxyl group-containing ethylenically unsaturated compound (m-2) is preferably 10 to 70 when the total of the monomers (M1) of the epoxy group-containing copolymer (P1) is 100 mol% Mole%, preferably 15 to 65 mole%. When the blending ratio of the carboxyl group-containing ethylenically unsaturated compound (m-2) is 10 mol% or more, sufficient curability can be exhibited when it is made into a photosensitive resin composition. In addition, if it is 70 mol% or less, the blending ratio of the monomer (M1) can be sufficiently ensured, and the ethylenically unsaturated resin (A1) having desired thermal decomposition resistance and the like can be obtained. In addition, the addition ratio of the carboxyl-containing ethylenically unsaturated compound (m-2) relative to the molar number of epoxy groups of the above-mentioned epoxy-containing copolymer (P1) is preferably 90 to 100%. Preferably, it is 95-100%. If the addition ratio of the carboxyl group-containing ethylenically unsaturated compound (m-2) is 90% or more, sufficient curability can be expressed when it is made into a photosensitive resin composition.

[Polyacid anhydride (d)] The polybasic acid anhydride (d) is not particularly limited as long as it has an acid anhydride structure having good reactivity with a hydroxyl group, and it is suitable to have a ring structure that does not generate by-products after the reaction. Specifically, 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, Methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, succinic anhydride, octenyl succinic anhydride, etc.

The reaction ratio of the polybasic acid anhydride (d), when the total of the monomers (M1) of the epoxy-containing copolymer (P1) is 100 mol%, it is preferably 10 to 70 mol%, preferably 15 ~65 mol%. The number of moles added to the carboxyl group-containing ethylenically unsaturated compound (m-2) is preferably 20 to 100 mole%, and more preferably 30 to 90 mole%.

[Method for manufacturing ethylenically unsaturated resin (A1)] The ethylenically unsaturated resin (A1) related to this embodiment can be obtained by adding a polymerization inhibitor and a catalyst to the solution of the epoxy-containing copolymer (P1), and then adding a carboxyl-containing ethylenic Saturated compound (m-2), make epoxy ring-opening addition reaction at 50～150℃, preferably 80～130℃, then add polybasic acid anhydride (d) if necessary to make addition reaction To make. The polymerization inhibitor is preferably carbon cluster (c).

When the carboxyl group-containing ethylenically unsaturated compound (m-2) is reacted, there is no problem in containing the solvent used in the above-mentioned copolymerization reaction. Therefore, the reaction can proceed without removing the solvent after the copolymerization reaction is completed. Here, the polymerization inhibitor is added in order to prevent the polymerization of the introduced double bond from colloiding.

[catalyst] The catalysts used in this embodiment include, for example, tertiary amines like triethylamine, quaternary ammonium salts like triethylbenzylammonium chloride, phosphorus compounds like triphenylphosphine, and chromium Chelating compounds, etc. These catalysts can be used alone or in combination of two or more. The amount of the catalyst used in this embodiment is not particularly limited. When the resin precursor (epoxy group-containing copolymer (P1)) is 100 parts by mass, it is generally 0.01-5 The part by mass is preferably 0.1 to 2 parts by mass, preferably 0.2 to 1 part by mass.

[Solvent used in the addition reaction] The solvent used in this embodiment is not particularly limited, and well-known solvents can be used appropriately. As the solvent, ether compounds, ketone compounds, ester compounds, aromatic hydrocarbon compounds, and carboxylic acid amide compounds can be used. The ether compound includes (poly)alkylene glycol monoalkyl ether; (poly)alkylene glycol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol Other ether compounds such as alcohol diethyl ether and tetrahydrofuran. Specific examples of (poly)alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol mono-n-propyl Ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether Propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. Specific examples of (poly)alkylene glycol monoalkyl ether acetate include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Specific examples of ketone compounds include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like. Specific examples of ester compounds include methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate , 2-hydroxy-3-methylbutyrate methyl ester, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-acetate Butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isobutyrate Propyl ester, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, ethyl 2-oxobutyrate, etc. Specific examples of aromatic hydrocarbon compounds include toluene, xylene and the like. Specific examples of the carboxylic acid amide compound include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and the like. These solvents can be used alone or in combination of two or more.

Among the above solvents, glycol ether-based solvents are preferred. That is, the solvent preferably uses (poly)alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether and (poly)alkylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate.

The amount of solvent used to manufacture the resin of this embodiment is not particularly limited. When the resin precursor is set to 100 parts by mass, it is generally 30-1000 parts by mass, preferably 50-800 parts by mass . As long as the amount of the solvent used is 1000 parts by mass or less, the viscosity of the resin can be controlled in an appropriate range, so it is suitable. On the other hand, if the amount of the solvent used is 30 parts by mass or more, it can prevent scorching during the reaction, and the synthesis reaction can proceed stably, so it is suitable. In addition, if the amount of the solvent used is 30 parts by mass or more, it is possible to prevent coloration or colloidization of the resin.

[Second Implementation Aspect] [Ethylene Unsaturated Resin (A2)] The ethylenically unsaturated resin (A2) related to this embodiment is a carboxyl group-containing copolymer (P2) as a carboxyl group-containing compound (b), which is a ring-opening addition to an epoxy group-containing compound (a) A resin containing a hydroxyl group and an ethylenically unsaturated group composed of an epoxy group of an epoxy group-containing ethylenically unsaturated compound (m-1). The carboxyl group-containing copolymer (P2) contains at least a structural unit derived from the carboxyl-containing ethylenically unsaturated compound (m-2), and if necessary, it contains a polymerizable monomer derived from a bridged cyclic hydrocarbon group with 10 to 20 carbon atoms. The structural unit of the body (m-3), or the structural unit derived from the polymerizable monomer (m-4) represented by the above general formula (1), or the polymerizable monomer (m-5) containing an aromatic ring Copolymers such as structural units.

The ethylenically unsaturated resin (A2) related to this embodiment can incorporate structural units derived from the addition reaction of an epoxy-containing ethylenically unsaturated compound (m-1) to introduce a double At the same time, the hydroxyl group can be obtained by opening the epoxy group. By this, light or thermosetting properties can be exhibited, and alkali developability can be exhibited. With this structural unit, the hardened product will exhibit sufficient hardness and exhibit high solvent resistance. In addition, by not allowing all the carboxyl groups in the carboxyl group-containing copolymer (P2) to react with the epoxy groups of the monomer (m-1) and leaving a part of them, the carboxylic acid can be introduced simultaneously.

As the epoxy-containing ethylenically unsaturated compound (m-1) related to this embodiment, the compound (m-1) related to the first embodiment can be used.

The addition ratio of the epoxy-containing ethylenically unsaturated compound (m-1) to the number of moles of carboxyl groups contained in the carboxyl-containing copolymer (P2) is preferably 90-100 mole%, preferably 95% ~100 mol%. When the addition ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is 90 mol% or more, sufficient curability can be expressed when it is made into a photosensitive resin composition. In addition, the reaction ratio of the epoxy group-containing ethylenic unsaturated compound (m-1) is 100 mol in total of all the monomers (M2) used in the epoxy group-containing copolymer (P2) %, preferably 10 to 70 mole%, preferably 15 to 65 mole%. If the blending ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is 10 mol% or more, sufficient curability can be exhibited when it is made into a photosensitive resin composition.

[Copolymer with carboxyl group (P2)] All monomers (M2) in the carboxyl group-containing copolymer (P2) (hereinafter also referred to as "copolymer (P2)") related to the ethylenically unsaturated resin (A2) of this embodiment, At least an ethylenically unsaturated compound containing a carboxyl group (m-2), and if necessary, a polymerizable monomer having a bridged cyclic hydrocarbon group with 10 to 20 carbon atoms (m-3), or the above chemical formula (1) The represented polymerizable monomer (m-4), or aromatic ring-containing polymerizable monomer (m-5), or other polymerizable monomer (m-6), etc.

The carboxyl-containing ethylenically unsaturated compound (m-2), polymerizable monomer (m-3), polymerizable monomer (m-4), and aromatic ring-containing polymerizable monomer (m-2) related to this embodiment m-5) and other polymerizable monomers (m-6) are the same as those described in the first embodiment, so the description is omitted.

[The ratio of the structure derived from each monomer in the carboxyl group-containing copolymer (P2)] All the monomers (M2) in the copolymer (P2) related to the present invention contain the ethylenically unsaturated compound (m-2) containing a carboxyl group, and if necessary, further contain a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms In the case of polymerizable monomer (m-3), or polymerizable monomer (m-4) represented by the above general formula (1), or polymerizable monomer (m-5) containing an aromatic ring, etc., The ratio of the structure derived from each monomer is a value using the molar ratio of each polymerizable monomer added for the copolymerization reaction. The blending ratio (molar ratio) of each monomer is not particularly limited. When the total of all the monomers (M2) is 100 mol%, the blending ratio of the monomer (m-2) is preferably 9 ~70 mol%, preferably 13-65 mol%. If the blending ratio of the monomer (m-2) is 9 mol% or more, sufficient curability can be exhibited when it is made into a photosensitive resin composition. If the blending ratio of monomer (m-2) is below 70 mol%, the blending ratio of monomer (m-3), or monomer (a-4), or monomer (m-5) is sufficient In many cases, an ethylenically unsaturated resin (A2) having desired thermal decomposition resistance can be obtained.

When the monomer (m-3) and/or monomer (m-4) is used, the blending ratio is 100 relative to the total amount of all monomers (M2) in the carboxyl group-containing copolymer (P2) Mole% is preferably more than 0 mol% to 40 mol% in total, preferably more than 0 mol% to 30 mol%. If the blending ratio is 1 mol% or more, the desired thermal decomposition resistance or thermal yellowing resistance and good solubility in solvents can be obtained.

In the case of using the monomer (m-5), the blending ratio is 100 mol% relative to the total amount of the carboxyl group-containing ethylenically unsaturated compound (m-2), and should exceed 0 mol% to 50 mol% Ear% is better, more than 0 mol%-40 mol% is more preferred. In the case of using the monomer (m-6), the blending ratio is 100 mol% relative to the total amount of the monomer (M2) of the epoxy-containing copolymer (P2), and exceeds 0 mol% -10 mol% is preferred, and more than 0 mol% to 5 mol% is preferred.

[Copolymerization reaction (Method for producing carboxyl group-containing copolymer (P2))] The carboxyl group-containing copolymer (P2) related to the present invention can be produced by copolymerization in the same manner as the copolymer (P1) related to the first embodiment.

[Method for manufacturing ethylenically unsaturated resin (A2)] The method of producing ethylenically unsaturated resin (A2) is to react an epoxy-containing ethylenic unsaturated compound (m-1) and a carboxyl-containing copolymer (P2) in the presence of a polymerization inhibitor and catalyst. In the method of producing the ethylenically unsaturated resin (A2), the aforementioned polymerization inhibitor is preferably the aforementioned carbon cluster (c).

An example of this embodiment is that the ethylenically unsaturated resin (A2) related to this embodiment can be added to the solution of the carboxyl group-containing copolymer (P2) as a polymerization inhibitor after carbon cluster (c) , An epoxy group-containing ethylenically unsaturated compound (m-1) is added, and it is produced by reacting it under the same conditions as the ring-opening addition reaction of the epoxy group in the first embodiment. The carbon cluster (c) and solvent used are the same as in the first embodiment.

[Third Implementation Aspect]

[Ethylene Unsaturated Resin (A3)] The ethylenically unsaturated resin (A3) used in this embodiment is a carboxyl-containing ethylenic unsaturated compound (m-2) as a carboxyl-containing compound (b), which is a ring-opening addition to an epoxy-containing The epoxy resin of the epoxy resin (P3) of the compound (a) is preferably a polybasic acid anhydride (d) which is further added to the hydroxyl group generated by the aforementioned epoxy group opening and contains a carboxyl group and ethylenic unsaturation. Based resin. Epoxy resin (P3) is composed of novolac epoxy resin (P3-1), bisphenol epoxy resin (P3-2), and bifunctional epoxy resin (P3-3) with a biphenyl skeleton The group is better. That is, the ethylenically unsaturated resin (A3) used in the embodiment of the present embodiment can be exemplified by the addition of a novolac type epoxy resin (P3-1) to an ethylenically unsaturated compound (m-2) containing a carboxyl group. It is necessary to further add polybasic acid anhydride (d) ethylenically unsaturated resin (A3-1); or add dibasic acid and carboxyl-containing ethylenic unsaturated compound (m) to bisphenol type epoxy resin (P3-2) -2), if necessary, further add polybasic acid anhydride (d) ethylenically unsaturated resin (A3-2); or add carboxyl-containing ethylenic resin to bifunctional epoxy resin (P3-3) with biphenyl skeleton The unsaturated compound (m-2) is further added with the ethylenically unsaturated resin (A3-3) of the polybasic acid anhydride (d) if necessary. The carboxyl group-containing ethylenically unsaturated compound (m-2), carbon cluster (c), catalyst, solvent used, etc. used in this embodiment aspect can be the compound of the first embodiment aspect.

[Ethylene Unsaturated Resin (A3-1)] Ethylene unsaturated resin (A3-1) can be added with carboxyl group-containing ethylenic unsaturated compound (m-2) to the novolac epoxy resin (P3-1) in order to introduce double bonds. It is produced by introducing a carboxyl group and adding a polybasic acid anhydride (d).

The novolac epoxy resin (P3-1) includes cresol novolac epoxy resin, phenol novolac epoxy resin, and the like. These novolac epoxy resins can be used alone or in two or more types.

[Ethylene Unsaturated Resin (A3-2)] Ethylene unsaturated resin (A3-2) can be added with carboxyl group-containing ethylenic unsaturated compound (m-2) to bisphenol epoxy resin (P3-2) in order to introduce double bonds. In order to introduce a carboxyl group, it is produced by adding a polybasic acid anhydride (d).

The bisphenol type epoxy resin (P3-2) includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. These bisphenol type epoxy resins can be used individually or in two or more types. Among these, from the viewpoint of availability and reactivity, bisphenol A epoxy resin is preferred.

[Ethylene Unsaturated Resin (A3-3)] Ethylene unsaturated resin (A3-3) can be added with carboxyl group-containing ethylenic unsaturated compound (m-2) in order to introduce double bond to bifunctional epoxy resin (P3-3) with biphenyl skeleton , And then add polybasic acid anhydride (d) as necessary to introduce carboxyl groups to produce. The bifunctional epoxy resin (P3-3) having a biphenyl skeleton is not particularly limited as long as it has a biphenyl skeleton in the molecule and two epoxy groups. Examples of the biphenyl skeleton include the structure represented by the following formula (5).

In the above formula (5), R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and E and E'are independent of each other and represent an organic group having an epoxy group.

Specific examples of the bifunctional epoxy resin having a biphenyl skeleton include YX4000 manufactured by Mitsubishi Chemical Co., Ltd. (in the following formula (6), R'is CH ₃ ), YX4000K (in the following formula (6), R'is CH ₃ ), YX4000H (in the following formula (6), R'is CH ₃ ), YL6121HA (in the following formula (6), a mixture of a compound in which R'is H and a compound in which R'is CH ₃ )Wait.

If necessary, an ethylenically unsaturated compound (m-2) containing a carboxyl group and a saturated monobasic acid may be added to the epoxy group of the ethylenically unsaturated resin (A3). The saturated monobasic acid is not particularly limited, and examples include formic acid, acetic acid, propionic acid, butyric acid, lauric acid, tridecyl acid, palmitic acid, and stearic acid. The saturated monobasic acid can be used alone or in two or more types. Among these, from the viewpoint of boiling point and reactivity, acetic acid and propionic acid are preferred. By making the ethylenically unsaturated resin (A3) in which the carboxyl-containing ethylenically unsaturated compound (m-2) and the saturated monobasic acid are added together, the flexibility is improved.

As the polybasic acid anhydride (d), the polybasic acid anhydride (d) described in the first embodiment can be used.

In the ethylenically unsaturated resin (A) used in the present invention, the carboxyl group derived from the polybasic acid anhydride (d) in the ethylenically unsaturated resin (A3) of this embodiment may be further added with an epoxy-containing ethylenic group Unsaturated compound (m-1). As the epoxy group-containing ethylenic unsaturated compound, the epoxy group-containing ethylenic unsaturated compound (m-1) described in the first embodiment can be used.

The reaction conditions required to obtain the ethylenically unsaturated resin (A3) or the epoxy resin (P3) used in the present invention may be appropriately set according to conventional methods. Addition reaction of ethylenically unsaturated compound (m-2) containing carboxyl group and saturated monobasic acid as necessary, for example, as long as each raw material, polymerization inhibitor and addition reaction catalyst are added to the solvent, the oxygen concentration is suitable 2-10% by volume, preferably a gas environment with an oxygen concentration of 5-7% by volume, preferably 100-140°C, preferably 110-130°C, for 2-12 hours. The addition reaction of an epoxy-containing ethylenically unsaturated compound is preferably in a gas environment with an oxygen concentration of 2-10% by volume, preferably an oxygen concentration of 5-7% by volume, preferably 100-140°C, preferably It can be carried out at 110-130°C for 2-10 hours.

The suitable structural unit ratio of the ethylenically unsaturated resin (A3) used in the present invention is as follows. In the ethylenically unsaturated resin (A3), the structural unit derived from the epoxy resin (P3) is 40 to 70 mass%, and the structural unit derived from the carboxyl-containing ethylenic unsaturated compound (m-2) is 5 to 35 mass% %. The structural unit derived from the polybasic acid anhydride (d) is 10-40% by mass. When a saturated monobasic acid is used, the structural unit derived from the saturated monobasic acid is more than 0 mol% and 20 mass% or less. In the case of using an epoxy-containing ethylenic unsaturated compound (m-1), the structural unit derived from the epoxy-containing ethylenic unsaturated compound (m-1) is more than 0 mol% and 10% by mass the following. In addition, when setting an appropriate ratio of structural units of the ethylenically unsaturated resin (A3) used in the present invention, structural units derived from the ethylenically unsaturated compound (m-2) containing a carboxyl group and saturated monobasic acid used as necessary The total addition rate of the epoxy groups contained in the structural unit derived from the epoxy resin (P3) is preferably 90 to 100% relative to the total epoxy groups. The structural unit derived from the polybasic acid anhydride is added to the The addition rate of the hydroxyl group produced by the addition of the carboxyl-containing ethylenically unsaturated compound (m-2) and the structural unit of the saturated monobasic acid used if necessary is preferably 5 to 80%, and 10 to 70% is more good. In addition, the addition rate of the structural unit derived from the epoxy group-containing ethylenically unsaturated compound (m-1) to the carboxyl group generated by the addition of the structural unit derived from the polybasic acid anhydride (d) is 10 to 50% is better.

[Method of manufacturing ethylenically unsaturated resin (A3)] The method of producing ethylenically unsaturated resin (A3) is to make epoxy resin (P3) and carboxyl-containing ethylenically unsaturated compound (m-2) react in the presence of a polymerization inhibitor and catalyst to produce ethylenically unsaturated resin In the method of resin (A3), the aforementioned polymerization inhibitor is preferably the aforementioned carbon cluster (c).

[Fourth Implementation Aspect]

[Ethylene Unsaturated Resin (A4)] The ethylenically unsaturated resin (A4) related to this embodiment is the ring-opening addition of the carboxyl-containing resin (P4) as the carboxyl-containing compound (b) to the epoxy-containing compound (a) An ethylenic unsaturated resin having a hydroxyl group composed of an epoxy group of an epoxy ethylenic unsaturated compound (m-1).

As the epoxy group-containing ethylenically unsaturated compound (m-1) used in this embodiment, the compound of the first embodiment can be used. The addition amount of the epoxy group-containing ethylenically unsaturated compound (m-1) is preferably more than 0 parts by mass and 10 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin (P4). If the addition amount of the epoxy group-containing ethylenically unsaturated compound (m-1) exceeds 0 parts by mass, the sensitivity can be improved, so it is suitable. On the other hand, as long as the addition amount of the epoxy group-containing ethylenically unsaturated compound (m-1) is 10 parts by mass or less, the elastic recovery rate and the developability can be maintained, so it is suitable. In the ethylenically unsaturated resin (A4), the molar ratio of the added epoxy-containing ethylenic unsaturated compound (m-1) to the structural unit derived from the carboxyl-containing resin (P4) is 0.05 to 0.3 Better.

[Resin containing carboxyl group (P4)] The carboxyl group-containing resin (P4) used in this embodiment is a resin having a carboxyl group obtained by reacting an epoxy resin (P3) with a polyfunctional carboxylic acid (e). The epoxy resin (P3) can use the epoxy resin (P3) used in the third embodiment.

[Multifunctional carboxylic acid (e)] The polyfunctional carboxylic acid (e) is not particularly limited. It may be either saturated or unsaturated polyfunctional carboxylic acid. Specifically, adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamic acid, secretory acid, etc. can be mentioned. The dibasic acid can be used alone or in two or more types. Among these, from the viewpoint of reactivity, adipic acid and itaconic acid are preferred.

[Proportion of structural units of carboxyl-containing resin (P4)] The carboxyl group-containing resin (P4) preferably contains 30 to 80% by mass of structural units derived from the epoxy resin (P3) and 20 to 70% by mass of structural units derived from the polyfunctional carboxylic acid (e). Here, in the carboxyl group-containing resin (P4), the molar ratio of the structural unit derived from the polyfunctional carboxylic acid (e) to the structural unit derived from the epoxy resin (P3) is preferably 0.1-0.8, and 0.15-0.7 is Better.

[Method for manufacturing carboxyl group-containing resin (P4)] The carboxyl group-containing resin (P4) used in this embodiment can be produced by, for example, the addition reaction of an epoxy resin (P3) and a polyfunctional carboxylic acid (e) in the presence of an addition catalyst. The conditions of the addition reaction required to obtain the carboxyl group-containing resin (P4) used in this embodiment may be appropriately set in accordance with a conventional method. For the addition reaction, for example, as long as the various raw materials and the addition catalyst are added to the solvent, the oxygen concentration is preferably 2-10% by volume, preferably in a gas environment with an oxygen concentration of 5-7% by volume, preferably 50-150°C. Preferably, it is performed at 60 to 140°C for 1 to 12 hours.

The solvent which can be used for the said addition reaction is not specifically limited, A well-known solvent can be used suitably. For example, the solvent used in the addition reaction of the first embodiment can be used. The polycondensation catalyst that can be used in the above addition reaction is not particularly limited, and a known catalyst can be appropriately used. For example, the catalyst used in the addition reaction of the first embodiment can be used.

[Method for manufacturing ethylenically unsaturated resin (A4)] The production method of ethylenically unsaturated resin (A4) is to make ethylene by reacting an epoxy-containing ethylenic unsaturated compound (m-1) with a carboxyl-containing resin (P4) in the presence of a polymerization inhibitor and a catalyst In the method of the unsaturated resin (A4), the aforementioned polymerization inhibitor is preferably carbon cluster (c). The carboxyl group-containing resin (P4) is a resin having a carboxyl group obtained by reacting an epoxy resin (P3) with a polyfunctional carboxylic acid (e).

An example of this embodiment is that the ethylenically unsaturated resin (A4) related to this embodiment can be added with carbon cluster (c) as a polymerization inhibitor to the solution of the aforementioned carboxyl-containing resin (P4). After the medium, an epoxy group-containing ethylenically unsaturated compound (m-1) is added, and the reaction is produced under the same conditions as the ring-opening addition reaction of the epoxy group in the first embodiment. The carbon cluster (c) and solvent used are the same as in the first embodiment.

[Fifth Implementation Aspect] [Ethylene Unsaturated Resin (A5)] The ethylenically unsaturated resin (A5) of this embodiment is an ethylenically unsaturated group formed by further adding the hydroxyl group of the above-mentioned ethylenically unsaturated resin (A2) to the polybasic acid anhydride (d) in the second embodiment. Of resin. The above-mentioned hydroxyl group is a hydroxyl group generated by ring-opening addition of the carboxyl group-containing copolymer (P2) to the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1).

The ethylenically unsaturated resin (A5) of this embodiment can be introduced into photosensitive by containing structural units derived from the addition reaction of an epoxy-containing ethylenically unsaturated compound (m-1) and a polybasic acid anhydride (d) A double bond with excellent properties and ring opening of an epoxy group can provide a hydroxyl group with excellent alkali developability. With this structural unit, the hardened product will exhibit sufficient hardness and exhibit high solvent resistance. In addition, by introducing an acidic group or a hydroxyl group as an alkali developable group, the affinity with the alkali developing solution of the copolymer is improved, a high-definition hardened pattern can be formed, and strict dimensional precision can be achieved. In addition, by not allowing all the carboxyl groups in the carboxyl group-containing copolymer (P2) to react with epoxy groups and leaving a part of them, carboxylic acid can be introduced at the same time. In addition, polybasic acid anhydrides can be added to the obtained hydroxyl groups to increase the amount of carboxylic acid introduced.

The reaction ratio of the epoxy-containing ethylenic unsaturated compound (m-1) to the epoxy-containing ethylenic unsaturated compound (m-1) of the ethylenic unsaturated resin (A2) of the second embodiment The reaction ratio is the same.

In the ethylenically unsaturated resin (A2), the ratio of the number of moles of the polybasic acid anhydride (d) to the epoxy group-containing ethylenically unsaturated compound (m-1) is preferably 10 to 90 mole%, more preferably It is 30 to 70 mole%. When the ratio of the polybasic acid anhydride (d) is 10 mol% or more, when it is made into a photosensitive resin composition, it can exhibit better curability. If it is 90 mol% or less, the unreacted product of the polybasic acid anhydride (d) does not remain, and the desired ethylenically unsaturated resin (A5) can be obtained. In addition, the reaction ratio of the polybasic acid anhydride (d) is based on the monomer (m-1), the monomer (m-2) constituting the carboxyl group-containing copolymer (P2), the optional monomer (m-3) and/ Or when the total of the monomer (m-4), any monomer (m-5), etc. is set at 100 mol%, it is preferably 5 to 65 mol%, and more preferably 5 to 50 mol%. If the blending ratio of the polybasic acid anhydride (d) is 5 mol% or more, when it is made into a photosensitive resin composition, it can exhibit better curability. If the blending ratio of the polybasic acid anhydride (d) is 65 mol% or less, a copolymer having a desired refractive index can be obtained.

[Method for manufacturing ethylenically unsaturated resin (A5)] The ethylenically unsaturated resin (A5) can be made by adding polybasic acid anhydride (d) after the production of the ethylenically unsaturated resin (A2). The acid anhydride (d) is produced by reacting.

When the polybasic acid anhydride (d) is reacted, there is no problem with containing the solvent used in the production of the ethylenically unsaturated resin (A2). Therefore, the solvent is not removed after the reaction to obtain the ethylenically unsaturated resin (A2) is completed. Removal can also proceed with the reaction.

[Sixth Implementation Aspect] [Ethylene Unsaturated Resin (A6)] The ethylenically unsaturated resin (A6) of this embodiment is an ethylenically unsaturated group formed by further adding the hydroxyl group of the above-mentioned ethylenically unsaturated resin (A4) in the fourth embodiment to a polybasic acid anhydride (d) Of resin. The above-mentioned hydroxyl group is a hydroxyl group generated by the ring-opening addition of the carboxyl group-containing resin (P4) to the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1).

The ethylenically unsaturated resin (A6) of this embodiment can be introduced into photosensitive by containing structural units derived from the addition reaction of epoxy-containing ethylenically unsaturated compounds (m-1) and polybasic acid anhydrides (d) A double bond with excellent properties and ring opening of an epoxy group can provide a hydroxyl group with excellent alkali developability. With this structural unit, the hardened product will exhibit sufficient hardness and at the same time exhibit high solvent resistance. In addition, by introducing an acidic group or a hydroxyl group as an alkali developable group, the affinity with the alkali developing solution of the copolymer is improved, a high-definition hardened pattern can be formed, and strict dimensional precision can be achieved. In addition, by not allowing all the carboxyl groups in the carboxyl group-containing resin (P4) to react with epoxy groups and leaving a part of them, the carboxylic acid can be introduced simultaneously. In addition, a polybasic acid anhydride can be added to the obtained hydroxyl group to increase the amount of carboxylic acid introduced.

The reaction ratio of the epoxy group-containing ethylenic unsaturated compound (m-1) to the epoxy group-containing ethylenic unsaturated compound (m-1) of the ethylenic unsaturated resin (A4) of the fourth embodiment The reaction ratio is the same.

The ratio of the number of moles of the polybasic acid anhydride (d) to the epoxy group-containing ethylenically unsaturated compound (m-1) is preferably 10 to 90 mole%, more preferably 30 to 70 mole%. When the ratio of the polybasic acid anhydride (d) is 10% by mole or more, when it is made into a photosensitive resin composition, it can exhibit better curability. If it is 90 mol% or less, the unreacted product of the polybasic acid anhydride (d) does not remain, and the desired ethylenically unsaturated resin (A6) can be obtained. In addition, the reaction ratio of the polybasic acid anhydride (d) relative to the ethylenically unsaturated resin (A6) is preferably more than 0% by mass and 10% by mass or less. If the addition amount of the polybasic acid anhydride (d) exceeds 0% by mass, the sensitivity can be improved, so it is suitable. On the other hand, as long as the addition amount of the polybasic acid anhydride (d) is 10% by mass or less, the elastic recovery rate and the developability can be maintained, so it is suitable.

[Method for manufacturing ethylenically unsaturated resin (A6)] The ethylenically unsaturated resin (A6) can be made by adding polybasic acid anhydride (d) after the production of the ethylenically unsaturated resin (A4). The acid anhydride (d) is produced by reacting.

When the polybasic acid anhydride (d) is reacted, there is no problem with containing the solvent used in the production of the ethylenically unsaturated resin (A4), so there is no need to remove it after the reaction to obtain the ethylenically unsaturated resin (A4) is completed The solvent can carry out the reaction.

[Characteristics of ethylenically unsaturated resin (A)] The molecular weight of the ethylenically unsaturated resin (A) obtained in the first to sixth embodiments of the present invention (weight average molecular weight in terms of polystyrene obtained by gel permeation chromatography (GPC)) is preferably It is 1,000 to 50,000, preferably 3,000 to 40,000. If the molecular weight is 1000 or more, the solvent resistance or thermal decomposition resistance of the cured film can be sufficiently ensured. On the other hand, if the molecular weight is below 50,000, the molecular weight or viscosity can be controlled within an appropriate range, which is practical. In addition, from the viewpoint of elastic recovery rate, the weight average molecular weight is preferably 3000 to 30,000.

The acid value (JIS K 6901 5.3) of the ethylenically unsaturated resin (A) is usually 20 to 300 KOH mg/g, preferably 30 to 200 KOH mg/g. As long as the acid value is 20KOHmg/g or more, the developability is good, so it is suitable. On the other hand, as long as the acid value is 300KOHmg/g or less, the exposed part (photohardened part) is not easily dissolved in the alkaline developing solution, so it is suitable. In addition, from the viewpoint of elastic recovery rate, the acid value of the ethylenically unsaturated resin (A) is preferably 30 to 200 KOHmg/g.

The hydroxyl equivalent of the ethylenically unsaturated resin (A) is usually 200 to 4000 g/mol, preferably 200 to 2500 g/mol. By setting the hydroxyl equivalent to 4000 g/mol or less, preferably 2500 g/mol or less, the water repellency of the alkaline developer can be suppressed, and good developability can be achieved. On the other hand, if the hydroxyl equivalent is less than 200 g/mol, the introduction amount of other substituents necessary for the present invention will decrease, and the desired curability, thermal decomposition resistance, thermal yellowing resistance, and refractive index may not be obtained. In addition, the hydroxyl equivalent in this specification is the mass of the ethylenically unsaturated resin (A) per mole of hydroxyl groups, and the theoretical value calculated from the charged amount of raw materials when the reaction rate is set to 100%.

In addition, the unsaturated group equivalent of the ethylenically unsaturated resin (A) is not limited as long as it can exert the desired effect of the present invention, and is usually 100 to 4000 g/mole, preferably 200 to 2000 g/mole. Preferably it is 300-500g/mol. As long as the unsaturated group equivalent is 100 g/mol or more, it is effective in improving the physical properties of the coating film and alkali developability, so it is suitable. On the other hand, as long as the unsaturated group equivalent is 4000 g/mol or less, it is effective in improving the sensitivity, so it is suitable. In addition, when the unsaturated group equivalent is 100 g/mol or more, it is effective for further improving the thermal decomposition resistance and thermal yellowing resistance. In addition, from the viewpoint of the elastic recovery rate, the unsaturated group equivalent of the ethylenically unsaturated resin (A) is preferably 200 to 2000 g/mole. In addition, in this specification, the unsaturated group equivalent is a theoretical value calculated from the loading amount when all the raw materials used for introducing the unsaturated group are assumed to react.

The epoxy equivalent of the ethylenically unsaturated resin (A) used in the present invention is not limited as long as it exerts the desired effect of the present invention, and is usually 100 to 4000 g/mole, preferably 200 to 2000 g/mole , Preferably 300～500g/mole. If the epoxy equivalent is 100 g/mol or more, it is effective in improving the physical properties of the coating film and the storage stability, and is suitable. Conversely, if the epoxy equivalent is 4000 g/mol or less, it is effective in further improving solvent resistance. In addition, the aforementioned epoxy equivalent refers to the mass of the polymer per mole of epoxy groups in the polymer. This value can be obtained by dividing the mass of the polymer by the amount of epoxy groups in the polymer (g/mole). In this specification, the "epoxy equivalent" refers to the loading amount of the raw material used for introducing epoxy groups and the loading amount of the carboxyl group-containing compound (b) for the addition reaction, and the reaction rate is set to 100% The calculated theoretical value.

[Solvent (B)] The solvent (B) of the ethylenically unsaturated resin composition is not particularly limited as long as it is a solvent that does not react with the ethylenically unsaturated resin (A). As the solvent (B), the same solvent as that used in the production of the ethylenically unsaturated resin (A) may be used, and the solvent contained after the reaction may be used as it is, or it may be further added. In addition, it may also be a solvent that coexists when other components are added. Specific examples of the solvent (B) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, and dipropylene glycol Monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate , Diethylene glycol ethyl ether acetate, etc. These can be used alone or in combination of two or more. In addition, among these, glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate used in the production of the ethylenically unsaturated resin (A) are preferred.

In the resin composition of this embodiment, the blending amount of the solvent (B) is generally 30 to 1000 parts by mass when the total of the components except the solvent (B) in the composition is 100 parts by mass , Preferably 50-800 parts by mass, more preferably 100-700 parts by mass. As long as the blending amount is in this range, it will become a resin composition having an appropriate viscosity.

[Reactive Diluent (D)] The reactive diluent (D) is not particularly limited, but preferably contains an ethylenically unsaturated double bond, preferably a vinyl group or a (meth)acryloxy group. Specific examples include styrene, α-methylstyrene, α-chloromethylstyrene, vinyl toluene, divinylbenzene, diallyl phthalate, diallyl phenyl phosphonate, etc. Aromatic vinyl monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate , Butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylic acid Ester, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol four (Meth) acrylic monomers such as (meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(meth)acrylate of ginseng (hydroxyethyl) isocyanurate, etc.; tricyanurate Allyl esters and so on. These can be used alone or in combination of two or more.

In the resin composition of this embodiment, the blending amount of the reactive diluent (D) is generally 10 to 100 parts by mass when the total of the components excluding the solvent (B) in the composition is 100 parts by mass. 90 parts by mass, preferably 20 to 80 parts by mass, more preferably 25 to 70 parts by mass. As long as the blending amount is in this range, it will become a resin composition with appropriate viscosity, and the photosensitive resin composition using it will have appropriate photocurability.

[Photosensitive resin composition] The photosensitive resin composition of the present invention contains ethylenically unsaturated resin (A), carbon cluster (c), solvent (B), reactive diluent (D), and photopolymerization initiator (E). The photosensitive resin composition of the present invention may further contain a coloring agent (F). In addition, the photosensitive resin composition of the present invention may not substantially contain a polymerization inhibitor other than the carbon cluster (c). "Substantially free" means that the content of a polymerization inhibitor other than the carbon cluster (c) is 0.010 parts by mass or less, preferably 0.05 parts by mass or less, relative to 100 parts by mass of the ethylenically unsaturated resin (A).

In the photosensitive resin composition of the present embodiment, the blending amount of the solvent (B) is generally 30 to 1,000 when the total of the components excluding the solvent (B) in the composition is 100 parts by mass. The parts by mass are preferably 50 to 800 parts by mass, more preferably 100 to 700 parts by mass. As long as the blending amount is in this range, it will become a photosensitive resin composition having an appropriate viscosity.

In the photosensitive resin composition of the present embodiment, the blending amount of the reactive diluent (D), when the sum of the components excluding the solvent (B) in the composition is 100% by mass, it is generally 10 to 90% by mass, preferably 20 to 80% by mass, more preferably 25 to 70% by mass. As long as the blending amount is in this range, the photosensitive resin composition will have an appropriate viscosity, and the photosensitive resin composition will have appropriate photocurability.

[Photopolymerization initiator (E)] The photopolymerization initiator (E) is not particularly limited. Specific examples include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenone, 2,2-dimethoxy- Acetophenones such as 2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-tertiary butyldiox-1-methylethyl)acetophenone; 2-methyl Anthraquinones such as anthraquinone, 2-pentyl anthraquinone, 2-tertiary butyl anthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diisopropyl Thioxanthones such as thioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-(1-third Benzophenones such as butyl dioxy-1-methyl ethyl) benzophenone, 3,3',4,4'-four (tertiary butyl dioxycarbonyl) benzophenone; 2-methyl -1-[4-(Methylsilyl)phenyl]-2-morpholinyl-propan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl ) Butanone-1; phosphine oxides; and xanthones. These can be used alone or in combination of two or more.

In the photosensitive resin composition of the present embodiment, the blending amount of the photopolymerization initiator (E) is generally 100 parts by mass when the sum of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass It is 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass. As long as the blending amount is in this range, it becomes a photosensitive resin composition having appropriate photocuring properties.

[Colorant (F)] The colorant (F) is not particularly limited as long as it is dissolved or dispersed in the solvent (B), and known dyes or pigments can be used. When a dye is used for the colorant (F), a coloring pattern with higher brightness can be obtained than when a pigment is used, and it also exhibits good alkali developability. On the other hand, when a pigment is used for the colorant (F), the heat resistance of the colored pattern is higher than when a dye is used. Dyes and pigments can be used together according to the required performance or the color of the target pixel.

"dye" Dyes, from the viewpoints of solubility in solvent (B) or alkaline developing solution, interaction of other components in the photosensitive resin composition, heat resistance, etc., acid dyes having acidic groups such as carboxyl groups, Salts of nitrogen compounds of acid dyes, sulfonamides of acid dyes, etc. are preferred. Specific examples of this dye include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and its derivatives. Among these, azo-based, xanthene-based, anthraquinone-based, or phthalocyanine-based acid dyes are preferred. These dyes can be used individually or in combination of two or more according to the color of the target pixel.

"pigment" Specific examples of pigments include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55 , 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; CI pigment blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; CI pigment violet 1, 19, 23 , 29, 32, 36, 38 and other purple pigments; CI Pigment Green 7, 36, 58 and other green pigments; CI Pigment Brown 23, 25 and other brown pigments; CI Pigment Black 1, 7, carbon black, titanium black, Black pigments such as iron oxide. These pigments can be used individually or in combination of two or more according to the color of the target pixel.

When the colorant (F) is blended in the photosensitive resin composition of this embodiment, the blending amount is when the total of the components other than the solvent (B) in the photosensitive resin composition is 100 parts by mass , Generally 5 to 80 parts by mass, preferably 5 to 70 parts by mass, preferably 10 to 60 parts by mass.

When a pigment is used as the colorant (F), from the viewpoint of improving the dispersibility of the pigment, a known dispersant may be blended into the photosensitive resin composition. As the dispersant, it is better to use a polymer dispersant with excellent dispersion stability over time. Examples of polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, and sorbitan fats Family ester dispersant, aliphatic modified ester dispersant, etc. This kind of polymer dispersant can also use products such as EFKA (manufactured by Efka Chemicals BV (EFKA)), Disperbyk (manufactured by BYK-Chemie), DISPARLON (manufactured by Kusumoto Chemical Co., Ltd.), and SOLSPERSE (manufactured by Zeneca) A commercially available product. The blending amount of the dispersant in the photosensitive resin composition of the present embodiment may be appropriately set in accordance with the type of pigment or the like used.

[Composition of ethylenically unsaturated resin composition] The blending amount of the ethylenically unsaturated resin (A), carbon cluster (c), and solvent (B) in the resin composition of this embodiment is set to 100 in the resin composition except for the solvent (B). In terms of parts by mass, ethylenically unsaturated resin (A) is preferably 50-99.9 parts by mass; carbon cluster (c) is preferably 0.00001-10 parts by mass; solvent (B) is preferably 30-1000 parts by mass, 50- 800 parts by mass is preferable, and 100 to 700 parts by mass is more preferable.

When the resin composition of this embodiment contains the reactive diluent (D), blending of the ethylenically unsaturated resin (A), carbon cluster (c), solvent (B), and reactive diluent (D) Amount, when the total of the components except the solvent (B) in the resin composition is 100 parts by mass, the ethylenically unsaturated resin (A) is 10 to 90 parts by mass, and the carbon cluster (c) is 0.00001 to 10 parts by mass. Parts, solvent (B) is 30 to 1000 parts by mass, reactive diluent (D) is 10 to 90 parts by mass, preferably ethylenically unsaturated resin (A) is 20 to 80 parts by mass, carbon cluster (c) is 0.0001 to 0.10 parts by mass, solvent (B) 50-800 parts by mass, reactive diluent (D) 20-80 parts by mass, preferably ethylenically unsaturated resin (A) 30-75 parts by mass, carbon cluster (c) 0.0005 -0.05 parts by mass, 100-700 parts by mass of solvent (B), and 25-70 parts by mass of reactive diluent (D). [Composition of photosensitive resin composition]

Blending amount of ethylenically unsaturated resin (A), carbon cluster (c), solvent (B), reactive diluent (D), and photopolymerization initiator (E) of the photosensitive resin composition of this embodiment , When the total of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass, it is preferably 5 to 80 parts by mass of the ethylenically unsaturated resin (A) and 0.00001 to 10 of the carbon cluster (c) Parts by mass, solvent (B) 30 to 1000 parts by mass, reactive diluent (D) 10 to 90 parts by mass, photopolymerization initiator (E) 0.1 to 30 parts by mass, preferably ethylenically unsaturated resin (A) ) 8 to 70 parts by mass, carbon cluster (c) 0.0001 to 5 parts by mass, solvent (B) 50 to 800 parts by mass, reactive diluent (D) 20 to 80 parts by mass, photopolymerization initiator (E) 0.5 -20 parts by mass, more preferably 10-60 parts by mass of ethylenically unsaturated resin (A), 0.005-1 parts by mass of carbon cluster (c), 100-700 parts by mass of solvent (B), reactive diluent (D) 25 to 70 parts by mass, and 1 to 15 parts by mass of the photopolymerization initiator (E).

When the photosensitive resin composition of this embodiment contains a colorant (F), ethylenically unsaturated resin (A), carbon cluster (c), solvent (B), reactive diluent (D), photopolymerization The blending amount of the initiator (E) and the coloring agent (F), generally speaking, when the total of the components other than the solvent (B) in the photosensitive resin composition is set to 100 parts by mass, the ethylenically unsaturated Resin (A) is 5 to 80 parts by mass, carbon cluster (c) is 0.00001 to 10 parts by mass, solvent (B) is 30 to 1000 parts by mass, reactive diluent (D) is 10 to 89 parts by mass, photopolymerization Starting agent (E) is 0.1-30 parts by mass, coloring agent (F) is 5-80 parts by mass, preferably ethylenically unsaturated resin (A) is 8 to 70 parts by mass, carbon cluster (c) is 0.0001 to 0.10 parts by mass Parts, 50 to 800 parts by mass of solvent (B), 20 to 80 parts by mass of reactive diluent (D), 0.5 to 20 parts by mass of photopolymerization initiator (E), 5 to 70 parts by mass of colorant (F), More preferably, ethylenically unsaturated resin (A) is 10-60 parts by mass, carbon cluster (c) is 0.0005-0.5 parts by mass, solvent (B) is 100-700 parts by mass, and reactive diluent (D) is 25-70 parts by mass. , Photopolymerization initiator (E) 1-15 parts by mass, and colorant (F) 10-60 parts by mass.

In the photosensitive resin composition of this embodiment, in addition to the above-mentioned components, well-known additives such as well-known coupling agents, leveling agents, and thermal polymerization inhibitors, and well-known coloring agents may be blended in order to impart predetermined characteristics. Or fillers, dispersants, etc. The blending amount of these additives is not particularly limited as long as it is in a range that does not inhibit the effects of the present invention.

[Method for manufacturing photosensitive resin composition] The photosensitive resin composition of this embodiment can be manufactured by mixing the above-mentioned components using a well-known mixing device. In addition, the photosensitive resin composition of this embodiment can first prepare a resin composition containing ethylenically unsaturated resin (A) and solvent (B), and then mix the reactive diluent (D) and photopolymerization initiator (E) to manufacture. In addition, this resin composition can be used for other purposes besides preparing the photosensitive resin composition of this embodiment.

[Resin Cured Film] The photosensitive resin composition of this embodiment contains the resin of this embodiment, and therefore has excellent developability, good colorant dispersibility and solvent resistance, and a cured film with high elastic recovery rate can be obtained. Therefore, the photosensitive resin composition of this embodiment is suitable as a material for a black matrix, a color filter, and a black column spacer. In addition, the photosensitive resin composition of the present embodiment has good coloring agent dispersibility, and even if it contains a black coloring agent, it can fully satisfy general characteristics such as developability, and can form adhesion to the formed surface. Good resin cured film. Therefore, according to the photosensitive resin composition of this embodiment, the adhesion to the surface to be formed is good, and the black pattern which has sufficient light-shielding property can be formed.

[Manufacturing method of resin cured film] The cured resin film of this embodiment can be manufactured by the method disclosed below, for example. First, a photosensitive resin composition is applied to the formed surface of the resin cured film to form a resin layer (coating film). Next, the resin layer is exposed via a mask of a predetermined pattern, and the exposed part is photocured. Next, the unexposed part of the resin layer is developed with a developer to produce a cured resin film having a predetermined pattern. Then, if necessary, post-baking (heat treatment) of the resin cured film is performed. When exposing the resin layer, a halftone mask with a predetermined pattern can also be used. In this case, the unexposed part and the semi-exposed part are developed with a developer to form a resin cured film having a predetermined pattern.

The method of applying the photosensitive resin composition is not particularly limited, and examples thereof include a screen printing method, a roll coating method, a curtain coating method, a spray coating method, and a spin coating method. After the photosensitive resin composition is coated, heating means such as a circulating oven, an infrared heater, a hot plate, etc. may be used as necessary to volatilize the solvent (B) contained in the resin layer. The heating conditions after coating are not particularly limited, as long as they are appropriately set in accordance with the composition of the photosensitive resin composition. For example, the heating temperature after coating can be set at 50°C to 120°C, and the heating time can be set at 30 seconds to 30 minutes.

The method of exposing the resin layer is not particularly limited, and examples include a method of irradiating active energy rays such as ultraviolet rays and excimer laser light. The amount of energy rays irradiated to the resin layer may be appropriately set in accordance with the composition of the photosensitive resin composition. For example, the amount of energy ray irradiated to the resin layer can be set at 30-2000 mJ/cm ² , but it is not limited by this range. The light source used for exposure is not particularly limited, and low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, etc. can be arbitrarily selected and used.

In order to obtain excellent developability, it is better to use an alkaline developer as the developer used for development. Examples of alkaline developing solutions include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; tetramethyl Ammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl- 4-amino-N-ethyl-N-β-methanesulfonamide ethyl aniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethyl aniline and the like Sulfate, hydrochloride, p-toluenesulfonate and other p-phenylenediamine-based compounds. The developer can also contain defoamers, surfactants, etc. as necessary.

After developing with the developer, it is better to wash the cured resin film with a predetermined pattern with water and dry it. In addition, it is preferable to perform post-baking (heat treatment) of a cured resin film having a predetermined pattern after development with a developer. By performing post-bake, the curing of the resin cured film can be performed more reliably. The conditions of post-baking are not particularly limited and can be arbitrarily selected as long as they are appropriately set in accordance with the composition of the photosensitive resin composition. For example, the heating temperature of post-bake can be set at 130℃～250℃. In addition, the heating time of post-bake is preferably 10 minutes to 4 hours, preferably 20 minutes to 2 hours.

[Image display device] The image display device of this embodiment includes the resin cured film of this embodiment. Specific examples of the image display device include, for example, a liquid crystal display device and an organic EL display device. For the image display device, for example, one or more members selected from a black matrix, a color filter, and a black column spacer are formed of the cured resin film of the present embodiment.

The material of the substrate on which the resin cured film is formed is not particularly limited, and examples include glass, silicon, polycarbonate, polyester, polyamide, polyimide, polyimide, and aluminum. , Printed circuit boards and other substrates with wiring patterns formed on the surface, array substrates, etc.

The manufacturing method of the image display device of this embodiment should just include the step of forming the resin cured film of this embodiment in accordance with the above-mentioned manufacturing method, and the member other than the member formed of a resin cured film can be manufactured according to the conventional method.

The cured resin film formed by curing the photosensitive resin composition of this embodiment has excellent developability, good colorant dispersibility and solvent resistance, and a high elastic recovery rate. Therefore, it is suitable as a material for a black matrix, a color filter, and a black column spacer included in an image display device. [Example]

The present invention will be described in detail below with reference to examples, but the present invention is not limited by these examples. In addition, in this embodiment, parts and percentages are all based on quality unless otherwise explained. [Example 1] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 137.5 g of propylene glycol monomethyl ether acetate was added, and nitrogen replacement was performed while stirring, and the temperature was raised to 120°C. Next, add to a monomer mixture containing 141.7 g (1.00 mol) of glycidyl methacrylate, 4.7 g (0.02 mol) of tricyclodecyl methacrylate, and 5.0 g (0.05 mol) of styrene 13.3 g of tert-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, PERBUTYL (registered trademark) O), was dropped from the dropping funnel into the aforementioned flask over 2 hours . After the dripping was completed, it was further stirred at 120°C for 2 hours to carry out a copolymerization reaction to produce an epoxy group-containing copolymer (P1) solution. 72.0 g of acrylic acid as a monomer (m-2) and 6.0 g of a trimethylbenzene solution containing 3% by mass of fullerene (manufactured by Frontier Carbon Corporation, nanom (registered trademark) mixST) as a polymerization inhibitor , 0.67 g (0.3 parts by mass) of triphenylphosphine as a catalyst, low-oxygen air injected with nitrogen gas is poured so that the oxygen concentration becomes 4 to 7 vol%, while heating at 110° C. for 10 hours. Then, it was confirmed that the acid value was 1.0KOHmg/g or less, and 15.6 g of tetrahydrophthalic anhydride as the polybasic acid anhydride (d) was charged and reacted at 110°C for 2 hours to obtain an ethylenic acid containing a solid content of 50% by mass. An ethylenically unsaturated resin composition of a solution of saturated resin (A1) (solid content acid value 32.4 KOHmg/g, weight average molecular weight 9400). In addition, the solid content means the heating residue after heating the ethylenically unsaturated resin (A1) solution at 130°C for 2 hours, and the ethylenic unsaturated resin (A1) is the main component. By measuring the acid value (residual monomer ratio) in the reaction solution and calculating the addition reaction rate of acrylic acid to the epoxy group, it was 99.1%.

[Examples 2 to 4 and Comparative Examples 1 to 3] In Examples 2 to 3, the amount of fullerene solution added was changed, and in Example 4, it was changed to an indene adduct of fullerene (manufactured by Frontier Carbon, nanom (registered trademark) spectra NPQ3000) The solution (concentration 0.02% by mass) was used instead of the fullerene solution. In the comparative example, BHT (di-tertiary butyl hydroxytoluene) was used instead of the fullerene solution. The composition of the solution of ethylenically unsaturated resin. The results are shown in Table 1. [Example 5] In Example 5, an ethylenically unsaturated resin solution was obtained in the same manner as in Example 1, except that the polymerization inhibitor was changed to 0.02% by mass of the soot-like substance. The soot-like substance was obtained by the following method. The ratio of toluene and pure oxygen was 3:1, and the mixture was supplied to the reaction tube and mixed, and heated under 67 hPa and 180° C. conditions to obtain coal. Next, washing was performed twice with toluene to obtain a soot-like substance. The results are shown in Table 1.

[Example 6] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 185.6 g of propylene glycol monomethyl ether acetate was added, and the mixture was replaced with nitrogen, while stirring, and the temperature was raised to 120°C. Next, add to the monomer mixture containing 58.5 g (0.68 mol) of methacrylic acid, 33.7 g (0.15 mol) of tricyclodecyl methacrylate, and 3.0 g (0.02 mol) of benzyl methacrylate 2.9 g of tert-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, PERBUTYL (registered trademark) O) was dropped from the dropping funnel into the aforementioned flask over 2 hours . After the dripping was completed, it was further stirred at 120°C for 2 hours to proceed with the copolymerization reaction to produce a carboxyl group-containing copolymer (P2) solution. 35 g of glycidyl methacrylate as a monomer (m-1) and 3% by mass of fullerene (manufactured by Frontier Carbon Corporation, nanom (registered trademark) mixST) as a polymerization inhibitor are contained therein 3.5 g of a benzene solution, 0.39 g (0.3 parts by mass) of triphenylphosphine as a catalyst, and low-oxygen air injected with nitrogen gas so that the oxygen concentration becomes 4% to 7%, while heating at 110° C. for 10 hours. Then, it was confirmed that the acid value was 72.0KOHmg/g or less, and an ethylenically unsaturated resin composition (solid content acid value 196.8KOHmg/g, solid content acid value 196.8KOHmg/g, The weight average molecular weight is 18500). By measuring the acid value in the reaction solution, the reaction rate of acid and epoxy was calculated, and the result was 97.8%.

[Examples 7-10 and Comparative Examples 4-6] In Examples 6 to 8, the addition amount of the fullerene solution was changed. In Example 9, the polymerization inhibitor was changed to an indene adduct of fullerene. In Example 10, the polymerization was inhibited. The agent was changed to a soot-like substance, and in the comparative example, an ethylenically unsaturated resin composition was obtained in the same manner as in Example 1, except that BHT was used instead of the fullerene solution. The results are shown in Table 2.

[Example 11] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, the cresol novolac epoxy resin N-695 manufactured by DIC Co., Ltd. as an epoxy resin (P3) (epoxy equivalent 215 ) 224.1 g and 94.5 g of PGMEA, and while pouring low-oxygen air into which nitrogen gas has been injected so that the oxygen concentration becomes 4 to 7% by volume, the temperature is raised to 120°C. Then it is confirmed that the acid value is 42.0 KOHmg/g or less, and 75.1 g (1.04 mol) of acrylic acid as the monomer (m-2) contains fullerene (manufactured by Frontier Carbon, nanom (registered trademark) mix ST) 3 8 g of a mass% trimethylbenzene solution was dissolved in 0.9 g of triphenylphosphine, and this was dropped in 10 minutes. Then, the reaction was continued until the acid value became less than 1, and 33.4 g of succinic anhydride as the polybasic acid anhydride (d) was charged and reacted at 110°C for 1 hour to obtain an ethylenically unsaturated resin (A3) with a solid content concentration of 38.5% by weight. -1) Ethylene unsaturated resin composition of the solution (solid acid value 60.8KOHmg/g, weight average molecular weight 5900). The reaction rate was calculated by measuring the acid value (residual monomer ratio) in the reaction solution, and the result was 99.1%.

[Examples 12-15 and Comparative Examples 7-9] In Examples 12 to 13, the amount of fullerene solution added was changed. In Example 14, the polymerization inhibitor was changed to an indene adduct of fullerene. In Example 15, the polymerization was inhibited. The agent was changed to a soot-like substance, and in the comparative example, an ethylenically unsaturated resin composition was obtained in the same manner as in Example 9 except that BHT was used instead of the fullerene solution. The results are shown in Table 3.

[Example 16] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 64.3 g (0.30 mol) of 1,2,4-cyclohexanetricarboxylic acid as a polyfunctional carboxylic acid (e) and As an epoxy resin, 67.1 g of AER-2603 (epoxy equivalent 188) manufactured by Asahi Kasei Co., Ltd., 0.54 g of triphenylphosphine, and 88.1 g of PGMEA, and low-oxygen air injected with nitrogen gas is poured so that the oxygen concentration becomes 4-7 vol. %, while heating to 120°C. Then it was reacted until the acid value became 138KOHmg/g or less to prepare a carboxyl group-containing resin (P4), and 50.7 g of glycidyl methacrylate as the monomer (m-1) was added with fullerene (Frontier Carbon company make, nanom (registered trademark) mix ST) 4.9 g of 3% by mass trimethylbenzene solution, and this was dropped over 10 minutes. After confirming that the acid value is 40KOHmg/g or less, adding 17.9 g of succinic anhydride as the polybasic acid anhydride (d), and reacting at 110°C for 1 hour to obtain an ethylenically unsaturated resin (A6) with a solid content concentration of 48.5% by weight The ethylenically unsaturated resin composition of the solution (solid acid value 107.8KOHmg/g, weight average molecular weight 6100). The reaction rate was calculated by measuring the acid value (residual monomer ratio) in the reaction solution, and the result was 95.4%.

[Examples 17-20 and Comparative Examples 10-12] In Examples 17 to 18, the amount of fullerene solution added was changed. In Example 19, the polymerization inhibitor was changed to an indene adduct of fullerene. In Example 20, the polymerization was inhibited. The agent was changed to a soot-like substance, and in the comparative example, an ethylenically unsaturated resin composition was obtained in the same manner as in Example 13 except that BHT was used instead of the fullerene solution. The results are shown in Table 4.

The ethylenically unsaturated resin contained in the synthesized ethylenically unsaturated resin composition was measured for acid value and molecular weight by the following method. [Measurement method of acid value] According to JIS K6901 5.3.2, a mixed indicator of bromothymol blue and phenol red is used for measurement. It means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid ethylenically unsaturated resin (A). In addition, the solid content is the heating residue measured after heating the sample at 130°C for 2 hours.

[Measurement method of weight average molecular weight (Mw)] Using gel permeation chromatography (GPC), the measurement was made under the following conditions, and the standard polystyrene conversion was performed. Column: Shodex (registered trademark) LF-804+LF-804 (manufactured by Showa Denko Co., Ltd.) Column temperature: 40℃ Sample: 0.2% tetrahydrofuran solution of copolymer Developing solvent: tetrahydrofuran Detector: Differential refractometer (Shodex (registered trademark) RI-71S) (manufactured by Showa Denko Co., Ltd.) Flow rate: 1mL/min

As shown in Tables 1 to 4, in the examples, it was possible to synthesize even if the amount of fullerene as the inhibitor was reduced, but in the comparative example, the amount of BHT was reduced, and the crosslinking of the double bond could not be suppressed , And colloidization occurred.

[Examples 21 to 52, Comparative Examples 13 to 20] Using the resins of Examples 1 to 20 and Comparative Examples 1, 4, 7, and 10, respectively, photosensitive resin compositions formed by combining the formulations shown in Tables 5 to 8 were produced. In addition, the blending amount of the resin in the table is described as the value of the solid content, and the solvent contained in the synthesis of the resin is described in total with the item of "solvent" in the table.

[Evaluation of OD value] Using the photosensitive resin compositions of Examples 21 to 36 and Comparative Examples 13 to 16 on a glass substrate, a coating film with a thickness of 1.5 μm was formed by a spin coating mechanism. Then, the produced coating film was heated at 90°C for 3 minutes to volatilize the solvent in the coating film. Next, the entire surface of the coating film was exposed using MultiLight ML-251D/B manufactured by Ushio Electric Co., Ltd. and an irradiating optical unit PM25C-100 (exposure amount 200 mJ/cm ² ) and photocured. After the irradiation, the OD value of the film that was post-cured at 230°C for 30 minutes was measured using an OD value meter 361T manufactured by X-rite. The results are shown in Table 9. The larger the OD value, the less light can pass through, and the better it is as a black matrix.

[Evaluation of the shape of the photoresist pattern] A coating film with a thickness of 2.5μm was produced in the same way as the evaluation of the OD value, and a mask with a line and gap pattern of 20μm in line width was formed on the coating film, using Ushio Electric Co., Ltd. The MultiLight ML-251D/B and the irradiating optical unit PM25C-100 were exposed to light (exposure amount 50mJ/cm ² ) to be photohardened. After the irradiation, development was performed with a 0.2% by mass potassium hydroxide aqueous solution for 120 seconds, and then post-baked at 230°C for 30 minutes to obtain a target pattern. The ratio of the area of the lower part of the pattern to the area of 5% height from the upper part down was defined as T/B, and the results are shown in Table 9. The closer the T/B is to 1, the closer to the target pattern shape, and the better.

[Evaluation of heat yellowing resistance] On a glass substrate, using the photosensitive resin compositions of Examples 37 to 52 and Comparative Examples 17 to 20, respectively, a composition composed of the formula combination disclosed in Table 6 was produced, and the composition was spin-coated The cloth machine makes a coating film with a thickness of 2.5μm. Then, the produced coating film was heated at 90°C for 3 minutes to volatilize the solvent in the coating film. Next, the entire surface of the coating film was exposed using MultiLight ML-251D/B manufactured by Ushio Electric Co., Ltd. and an irradiating optical unit PM25C-100 (exposure amount 50 mJ/cm ² ) and photocured. After the irradiation, for the film that was post-cured at 230°C for 30 minutes, the absorbance of the resin cured film at the maximum absorption wavelength was measured using a UV spectrometer UV-1650PC manufactured by SIMAZU. The results are shown in Table 10. The smaller the ΔEab, the less yellowing, and the better.

[Assessment of Transparency] A coating film was produced in the same manner as the evaluation of heat yellowing resistance, and the transmittance at a wavelength of 380 nm to 780 nm was measured. The average value of the transmittance of each wavelength is defined as the average transmittance (%). The results of Examples 37 to 44 and Comparative Examples 17 and 18 are shown in Table 11. The results of Examples 45 to 52 and Comparative Examples 19 and 20 are shown in Table 12.

As shown in Tables 9 to 10, it can be seen that the photosensitive resin containing the carbon cluster (c) can obtain a cured product having excellent dispersibility of the colorant, excellent pattern shape, and heat-resistant yellowing resistance. In addition, as shown in Table 11 and Table 12, the transparency of the photosensitive resin using the ethylenically unsaturated resin synthesized with the carbon cluster (c) is improved.

Claims (13)

An ethylenically unsaturated resin composition characterized by containing: Ethylene unsaturated resin (A), Carbon cluster (c), and Solvent (B), The carbon cluster (c) is at least one of fullerenes and soot-like substances, and its content is 0.00001-10 parts by mass relative to 100 parts by mass of the ethylenically unsaturated resin (A). The ethylenically unsaturated resin composition of claim 1, wherein the aforementioned ethylenically unsaturated resin (A) is an ethylenically unsaturated compound (m-2) containing a carboxyl group by ring-opening addition to an epoxy-containing copolymer ( The epoxy group of P1), and the polybasic acid anhydride (d) is added to the ethylenically unsaturated resin (A1) formed by the addition of the hydroxyl group generated by the ring opening of the epoxy group, and the epoxy group-containing copolymer (P1) It contains a structural unit derived from an epoxy-containing (meth)acrylate (m-1), and a polymerizable monomer (m-3) selected from a bridged cyclic hydrocarbon group having 10 to 20 carbons A copolymer of at least one of the structural unit and the structural unit derived from the polymerizable monomer (m-4) represented by the following chemical formula (1),

(X and X'in the formula (1) are each independent and represent a hydrogen atom, a linear or branchable hydrocarbon group with 1 to 4 carbons, R1 and R2 are each independent, and each is a hydrogen atom, a carboxyl group or a carbon that may have a substituent The hydrocarbon group of 1-20 may also adopt a cyclic structure connecting R1 and R2). The ethylenically unsaturated resin composition of claim 1, wherein the aforementioned ethylenically unsaturated resin (A) is a carboxyl group-containing copolymer (P2) ring-opening addition to an epoxy group-containing ethylenically unsaturated compound (m- 1) The hydroxy-containing unsaturated group-containing ethylenic unsaturated resin (A2) composed of epoxy groups, and the aforementioned carboxyl-containing copolymer (P2) is derived from the carboxyl-containing ethylenic unsaturated compound (m- 2) The structural unit, and a structural unit selected from a polymerizable monomer (m-3) having a bridged cyclic hydrocarbon group with 10 to 20 carbons, and a polymerizable monomer represented by the following chemical formula (1) (m-4) A copolymer of at least one of the group consisting of structural units,

(X and X'in the formula (1) are each independent and represent a hydrogen atom, a linear or branchable hydrocarbon group with 1 to 4 carbons, R1 and R2 are each independent, and each is a hydrogen atom, a carboxyl group or a carbon that may have a substituent The hydrocarbon group of 1-20 may also adopt a cyclic structure connecting R1 and R2). The ethylenically unsaturated resin composition of claim 1, wherein the aforementioned ethylenically unsaturated resin (A) is an ethylenically unsaturated compound (m-2) containing a carboxyl group and added to the ring of the epoxy resin (P3) An oxy group, and an ethylenically unsaturated resin (A3) in which a polybasic acid anhydride (d) is added to the hydroxyl group generated by the opening of the epoxy group, and The aforementioned epoxy resin (P3) is At least one selected from the group consisting of novolac epoxy resin (P3-1), bisphenol epoxy resin (P3-2), and bifunctional epoxy resin (P3-3) having a biphenyl skeleton. The ethylenically unsaturated resin composition of claim 1, wherein the aforementioned ethylenically unsaturated resin (A) is a carboxyl-containing resin (P4) which is ring-opened and added to an epoxy-containing ethylenic unsaturated compound (m-1 ) Is an ethylenically unsaturated resin (A4) with a hydroxyl group, and The aforementioned carboxyl group-containing resin (P4) is a carboxyl group-containing resin obtained by reacting an epoxy resin (P3) with a polyfunctional carboxylic acid (e), The aforementioned epoxy resin (P3) is selected from novolac epoxy resin (P3-1), bisphenol epoxy resin (P3-2), and bifunctional epoxy resin (P3-3) with a biphenyl skeleton. At least one of the formed group. The ethylenically unsaturated resin composition of claim 1, wherein the aforementioned ethylenically unsaturated resin (A) is Polybasic acid anhydride (d) is added to the ethylenically unsaturated resin (A5) of the ethylenically unsaturated resin (A2) as in claim 3, or An ethylenically unsaturated resin (A6) in which a polybasic acid anhydride (d) is added to the hydroxyl group of the ethylenically unsaturated resin (A4) of claim 5. The ethylenically unsaturated resin composition of claim 1 or 2, wherein the aforementioned carbon cluster (c) is an unsubstituted fullerene. The ethylenically unsaturated resin composition of claim 1 or 2, which contains substantially no polymerization inhibitor other than the carbon cluster (c). The ethylenically unsaturated resin composition of claim 1 or 2, which further contains a reactive diluent (D). A photosensitive resin composition, which contains: Such as the ethylenically unsaturated resin composition of any one of claims 1-9, and Photopolymerization initiator (E). The photosensitive resin composition of claim 10, which further contains a colorant (F), The colorant (F) is at least one selected from the group consisting of dyes and pigments. The photosensitive resin composition of claim 10 or 11, which contains substantially no polymerization inhibitor other than the carbon cluster (c). A photoresist using the photosensitive resin composition according to any one of claims 10 to 12.